CN106007297B - Mercury-containing sludge heat treatment method - Google Patents
Mercury-containing sludge heat treatment method Download PDFInfo
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- CN106007297B CN106007297B CN201610602374.XA CN201610602374A CN106007297B CN 106007297 B CN106007297 B CN 106007297B CN 201610602374 A CN201610602374 A CN 201610602374A CN 106007297 B CN106007297 B CN 106007297B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/60—Combinations of devices covered by groups B01D46/00 and B01D47/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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Abstract
The invention discloses a mercury-containing sludge heat treatment method which is characterized in that mercury-containing sludge with the water content of more than 90% is sequentially treated by a sludge conditioner with a heating function, a dehydrator, a screw conveyor, a pyrolysis unit, a dust remover, a spray condensing device, a coalescer and a tail gas treatment device, wherein the treatment by the pyrolysis unit sequentially comprises drying treatment, pyrolysis treatment and combustion treatment of the sludge. The method comprises the following steps of firstly pretreating the mercury-containing sludge, feeding the pretreated sludge into a pyrolysis unit, circularly feeding pyrolysis gas formed by pyrolysis and combustion of the sludge into a drying section for utilization, converting mercury and compounds in the sludge into mercury vapor, and then introducing the mercury vapor into a dedusting and condensing unit to recover liquid mercury. The invention adopts the pyrolysis technology to carry out harmless treatment on the sludge, recycles heat energy, reduces the energy consumption of sludge treatment, prevents mercury pollution, produces byproducts with certain value, and has economic benefit and social value.
Description
Technical Field
The invention belongs to the field of oil and gas field energy environment protection, and particularly relates to a thermal treatment method of mercury-containing sludge.
Background
In recent years, with the development of natural gas industry in China, a large amount of mercury-containing sludge is produced in domestic mercury-containing gas fields every year, and an indispensable important process link is adopted in an oil-gas field treatment system during treatment of mercury-containing oil-containing sludge. If the mercury-containing sludge in the oil and gas field cannot be treated in time to cause serious secondary pollution, mercury is a toxic heavy metal and is defined as a class I (extremely harmful) poison by GBZ230-2010 'occupational toxicant hazard degree classification', and mercury and various compounds thereof have high toxicity, can generate a series of serious health influences on human brains and nervous systems, and cause serious harm to human reproductive capacity, organs and the like. The traditional sludge treatment methods such as landfill, sludge composting or sludge incineration and the like cannot meet the treatment of mercury-containing sludge, and the newly developed biological treatment process is immature. By using the method and the device, mercury in different forms in the mercury-containing sludge can be comprehensively recovered, so that the pyrolysis treatment process of the mercury-containing sludge becomes a treatment trend of the sludge according to national policies of harmlessness, resource utilization, energy conservation, consumption reduction and environmental protection.
Disclosure of Invention
The invention aims at the problems of the sludge treatment process, carries out treatment research on the mercury-containing sludge, provides a heat treatment method for the mercury-containing sludge, has feasibility and economy, carries out full harmless, reduction and resource utilization on the mercury-containing sludge, reduces the harm and influence of mercury on personnel and environment, reduces the sludge treatment energy consumption, and produces valuable byproducts.
In order to solve the technical problems, the invention adopts the following technical scheme
The mercury-containing sludge with the water content of more than 90% sequentially passes through a sludge conditioner with a heating function, a dehydrator, a screw conveyor, a pyrolysis unit, a dust remover, a spray condensing device, a coalescer and a tail gas treatment device, wherein the treatment of the pyrolysis unit sequentially comprises drying treatment, pyrolysis treatment and combustion treatment of the sludge, and the tail gas treatment device uses sulfur-loaded active carbon.
As a further improvement, a flocculating agent and a dispersing agent are added during sludge conditioning, partial oil stains in the sludge are removed, and the subsequent dehydration performance of the sludge is improved.
The dehydrator adopts a stacked spiral sludge dehydrator with good dehydration effect and strong economy.
The pyrolysis furnace adopts a multi-stage furnace, and the multi-stage furnace pyrolysis has the characteristics of low energy consumption, simple oxygen control operation, high efficiency, low operation cost, small occupied area and the like.
The dry dust remover adopts a filter drum type dust remover with high dust removal precision.
The spraying condensing system adopts a direct spraying mode to cool the pyrolysis flue gas and recover liquid mercury therein.
The tail gas treatment device adopts a demercuration tower with sulfur-carrying active carbon as a filler.
And mercury in the bottom of the settling tank needs to enter a mercury collecting box after excessive moisture is removed by the cyclone separator.
A method for pyrolyzing sludge comprises feeding mercury-containing sludge into a sludge conditioner through feeding equipment, and adding hot water, a dispersing agent and a demulsifier to thoroughly separate silt and oil in the sludge; the floating oil on the upper part of the conditioner is collected into an oil storage tank under the action of a floating oil collecting device, sludge discharged from the bottom of the conditioner tank enters a dehydrator for sludge-water separation, a fully dissolved flocculating agent is added at the upstream of the dehydrator, the water content of the dehydrated sludge is lower than 80%, and the sludge discharged from the bottom of the dehydrator is pumped to a subsequent heat treatment device. And the sewage separated by the dehydrator enters a sewage tank.
The pretreated mercury-containing sludge is conveyed to a sludge bin through a sealed screw conveyor, then enters a pyrolysis device, and is conveyed to a drying system at first, so that the moisture in the sludge is further removed, and the dried sludge with the moisture content of about 30% enters a pyrolysis furnace for pyrolysis treatment. Pyrolyzing sludge in a pyrolysis furnace at the pyrolysis temperature of 400-650 ℃ and the vacuum degree of the pyrolysis furnace of about 85kPa, and pyrolyzing and converting mercury, compounds and partial organic matters in the sludge into gas phase at the stage; the second stage is a combustion stage: and the gas phase and the carbon solid phase generated after pyrolysis enter a combustion chamber of the pyrolysis furnace again, the temperature of the combustion chamber is about 850-1000 ℃, ash generated by combustion is discharged from the bottom of the pyrolysis device, and combustion flue gas enters a drying section to dry the dewatered sludge. During the reaction, proper fuel gas can be introduced into the pyrolysis furnace to stabilize the pyrolysis temperature.
The mercury-containing flue gas generated in the pyrolysis device enters a dust remover, the flue gas after dust removal enters a spray cooling device for cooling, the flue gas after dust removal is cooled to about 40 ℃, the mercury vapor and the water vapor are condensed into liquid and then enter a settling tank, and the mercury at the lower part of the settling tank enters a mercury collecting tank after passing through a cyclone. And the sewage at the upper part of the settling tank enters a cooling circulating water system. And the tail gas discharged by the condenser enters a tail gas purification device, a coalescer and a mercury adsorption tower are arranged in the tail gas purification device, and finally the cleaned tail gas is discharged into the atmosphere, which is superior to the comprehensive emission standard of atmospheric pollutants (GB 16297-1996).
The invention has the beneficial effects that:
compared with the prior mercury-containing waste treatment technology, the invention has obvious beneficial effects, and the technical scheme shows that: before pyrolysis treatment is carried out on the mercury-containing sludge, a proper chemical reagent and a dehydrator are selected to carry out a pretreatment process on the mercury-containing sludge, so that the water content is reduced, the subsequent treatment is facilitated, and the energy consumption is saved; then, high-temperature pyrolysis is adopted to change mercury and compounds thereof contained in the sludge into mercury vapor, the mercury-containing high-temperature flue gas is used for drying the sludge after being combusted, and then a filter cartridge dust remover is adopted to remove dust from the mercury-containing flue gas, so that mercury-containing suspended matters are prevented from being generated in a subsequent condensation stage; and (3) recovering mercury in the flue gas by adopting air cooling and spraying two-stage cooling, and finally introducing the waste gas into a demercuration tower with sulfur-loaded activated carbon as a filler. The thermal treatment method for the mercury-containing sludge provided by the invention adopts a pyrolysis technology, has a simple and reasonable process, fully harmlessly and resourcefully utilizes the sludge, effectively recycles mercury in different forms and valence states, recycles heat energy by using high-temperature flue gas for drying the sludge, reduces energy consumption, effectively controls the environmental pollution problem of random stacking of the mercury-containing sludge, and has economic benefits and social benefits.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a process flow diagram of the present invention.
In the figure: 1-a dosing device, 2-a sludge conditioner, 3-a slurry pump, 4-a dehydrator, 5-a screw conveyer, 6-a sludge bin, 7-a pyrolysis device, 8-a dry dust collector, 9-a spray condensing device, 10-a coalescer, 11-a tail gas treatment device, 12-a settling tank, 13-a cyclone, 14-a mercury collecting tank, 15-a circulating pump, 16-a sewage tank, 17-a water transfer pump, 18-an oil storage tank, 19-an oil transfer pump and 20-a cooling circulating water system.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
FIG. 1 shows an example of the present invention, in which the mercury-containing sludge treatment scale is 1m3D (oil, water and mercury), sludge total mercury content: more than 200 mg/kg; oil content of sludge: not more than 10% (material before entering the dewatering machine), sludge moisture content: not less than 90 percent.
The mercury concentration in the waste residue leachate generated after the pyrolysis of the mercury-containing sludge is less than 0.1mg/L, and alkyl mercury cannot be detected. If the waste residue is used as agricultural sludge, the maximum allowable content of mercury and compounds thereof in the waste residue is 5mg/kg, and the waste residue can also be used as building materials or biochar. The mercury content in the tail gas discharged by the device is required to be less than 0.012mg/m3。
The heat treatment scheme comprises three processes of pretreatment, heat treatment and tail gas treatment. The mercury-containing sludge with the water content of more than 90 percent enters a sludge conditioner 2, and the silt and oil in the sludge are thoroughly separated by adding hot water, a dispersing agent and a demulsifier, wherein the water content of the oil is lower than 10 percent, and the oil content of the silt is lower than 2 percent; the floating oil on the upper part of the conditioner 2 is collected into an oil storage tank 18 under the action of a floating oil collecting device, and the separated dirty oil is conveyed into the oil storage tank 18 through an oil conveying pump 19; and (3) sludge discharged from the bottom of the conditioner 2 enters a dehydrator 4 for sludge-water separation, a fully dissolved flocculant is added at the upstream of the dehydrator 4, the water content of the dehydrated sludge is lower than 80%, and the sludge discharged from the bottom of the dehydrator is pumped to a subsequent heat treatment device. The sewage separated by the dehydrator 4 enters a sewage tank 16 and is transmitted to a gas field water tank or a water inlet buffer tank of a mercury-containing sewage treatment device through a water transfer pump 17.
The pretreated mercury-containing sludge is conveyed to a sludge bin 6 through a sealed screw conveyor 5 and then enters a pyrolysis device 7, and the pyrolysis device 7 is divided into three stages: a drying stage, a thermal stage and a combustion stage. Firstly, the sludge with the water content of about 80 percent is sent to a drying section, the water in the sludge is further removed, and the dried sludge with the water content of about 30 percent enters a pyrolysis section for pyrolysis treatment. Firstly, pyrolyzing sludge in a pyrolysis section at the pyrolysis temperature of 400-650 ℃, the vacuum degree of a pyrolysis furnace of 85kPa for about 40min, wherein mercury, compounds and organic matters in the sludge are pyrolyzed and converted into gas phase in the pyrolysis section; the second stage is a combustion stage: and the gas phase and the carbon solid phase generated after pyrolysis enter a combustion chamber of the pyrolysis furnace again for full combustion to remove residual harmful substances, the temperature of a combustion section is about 850-1000 ℃, ash generated by combustion is discharged from the bottom of the pyrolysis device, and combustion flue gas enters a drying section to dry the dewatered sludge. During the reaction, proper fuel gas can be introduced into the pyrolysis furnace to stabilize the pyrolysis temperature.
The mercury-containing flue gas generated in the pyrolysis device enters a dry type dust collector 8, the dust removal rate reaches 99.5%, the flue gas after dust removal enters a spray cooling device 9 for cooling, the temperature of the flue gas after dust removal is reduced to about 40 ℃, the mercury vapor and the water vapor are condensed into liquid and then enter a settling tank 12, and the mercury at the lower part of the settling tank 12 enters a mercury collecting tank 14 after passing through a cyclone 13. The sewage at the upper part of the settling tank 12 enters a cooling circulating water system 20.
The tail gas discharged by the spraying and condensing device 9 sequentially enters the coalescer 10 and the tail gas purification device 11, harmful substances such as mercury, dioxin, odor and the like in the tail gas can be removed, and finally the cleaned tail gas is discharged into the atmosphere.
The chemical reagents used in the pretreatment are polymeric ferric chloride, polyacrylamide and a dispersing agent, the dosage of the polymeric ferric chloride is 2000-2500 mg/L, the dosage of the polyacrylamide is 30 ppm-200 mg/L, the dispersing agent is prepared by matching a high-efficiency cationic surfactant, a strong penetrating agent and the like, and the dosage is 100-200 mg/L. A certain amount of catalyst needs to be added into the pyrolysis furnace to accelerate the cracking reaction of the sludge and reduce the reaction temperature, and the type of the catalyst which can be added is Fecl3，Na2CO3And metal oxides and the like.
The key equipment technical parameters and basic selection types of the mercury-containing sludge treatment device are shown in Table 1
TABLE 1 Key Equipment essential elements and parameters
The multi-stage furnace adopted by the invention consists of a plurality of even more than ten circular hearths which are overlapped in parallel in the horizontal direction, and sludge enters from the furnace body top furnace layer. The rabble arms with rabble teeth push the solid raw material in each hearth layer, and push the material (called as an 'inner rake hearth') from the outside to the center along a spiral path, and drop into the next hearth at the center. In the next adjacent hearth, the rake arms follow a spiral path from the center to the outside to push the material to the furnace wall (called "outer rake hearth") and fall into the next hearth through a series of blanking holes arranged near the furnace wall. In this manner, the solid material continues to move below the multi-stage furnace and is eventually discharged from the lowermost hearth. The gaseous material in the form of hot combustion products flows downwards in counter-current fashion to the upper part of the respective furnace, flowing out of the top furnace.
Compared with traditional pyrolysis equipment such as a rotary kiln, the multi-stage furnace has the characteristics of self-heating balance, no need of adding auxiliary fuel, low energy consumption, low power demand, small fly ash amount, easy layered control of the temperature in the furnace and the like, and has been successfully applied to sludge pyrolysis abroad.
Claims (3)
1. A method for pyrolyzing mercury-containing sludge produced in an oil-gas field is characterized in that the mercury-containing sludge enters a sludge conditioner through feeding equipment, and silt and oil in the sludge are thoroughly separated by adding hot water, a dispersing agent and a demulsifier; collecting the floating oil on the upper part of the conditioner into an oil storage tank under the action of a floating oil collecting device, feeding the sludge discharged from the bottom of the conditioner into a dehydrator for sludge-water separation, adding a fully dissolved flocculating agent at the upstream of the dehydrator, wherein the water content of the dehydrated sludge is lower than 80%, pumping the sludge discharged from the bottom of the dehydrator to a subsequent heat treatment device, and feeding the sewage separated by the dehydrator into a sewage tank;
the method comprises the following steps of conveying pretreated mercury-containing sludge to a sludge bin through a sealed screw conveyor, then conveying the sludge into a pyrolysis device, firstly conveying the sludge with the water content of 80% to a drying system, further removing water in the sludge, conveying the dried sludge with the water content of 30% into a pyrolysis furnace for pyrolysis treatment, pyrolyzing the sludge in the pyrolysis furnace at the pyrolysis temperature of 400-650 ℃ and the vacuum degree of the pyrolysis furnace of 85kPa, and at this stage, pyrolyzing mercury, compounds of the mercury and part of organic matters in the sludge to convert the mercury into a gas phase; the second stage is a combustion stage: the gas phase and the carbon solid phase generated after pyrolysis enter a combustion chamber of the pyrolysis furnace again, the temperature of the combustion chamber is 850-1000 ℃, ash generated by combustion is discharged from the bottom of the pyrolysis device, combustion flue gas enters a drying section to dry dewatered sludge, appropriate fuel gas is introduced into the pyrolysis furnace during reaction, and the pyrolysis temperature is stabilized;
the method comprises the following steps that mercury-containing flue gas generated in a pyrolysis device enters a dust remover, the flue gas after dust removal enters a spray cooling device for cooling, the temperature of the flue gas after dust removal is reduced to 40 ℃, mercury vapor and water vapor are condensed into liquid and then enter a settling tank, mercury at the lower part of the settling tank enters a mercury collecting tank after passing through a cyclone, sewage at the upper part of the settling tank enters a cooling circulating water system, tail gas discharged by a condenser enters a tail gas purification device, a coalescer and a mercury adsorption tower are arranged in the tail gas purification device, and finally the cleaned tail gas is discharged into the atmosphere and is superior to the comprehensive emission standard of atmospheric pollutants GB 16297-.
2. The method for pyrolyzing mercury-containing sludge produced in oil and gas fields according to claim 1, wherein the tail gas purification device adopts a sulfur-loaded activated carbon mercury adsorbent to remove mercury, dioxin and odor in the tail gas.
3. The method for pyrolyzing sludge containing mercury produced in oil and gas fields according to claim 1, wherein a catalyst is added into the pyrolysis furnace to accelerate the pyrolysis reaction of the sludgeThe reaction temperature is reduced, and the catalyst is FeCl3，Na2CO3And metal oxides.
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| CN106316035A (en) * | 2016-10-20 | 2017-01-11 | 佛山慧创正元新材料科技有限公司 | Method of recycling mercury in sludge polluted by mercury through heat treatment |
| CN106746419A (en) * | 2017-03-07 | 2017-05-31 | 盘锦宁泰能源科技有限公司 | A kind of oily sludge industrially scalable pyrolysis treatment systems and method |
| CN108085495A (en) * | 2017-12-05 | 2018-05-29 | 贵州重力科技环保有限公司 | A kind of method that oxygen-enriched air smelting efficiently separates recycling antimony mercury |
| CN109967486A (en) * | 2018-12-21 | 2019-07-05 | 中国科学院北京综合研究中心 | The device and method of the mercurous flying dust of zero discharge treatment |
| CN109824227B (en) * | 2019-03-18 | 2019-11-15 | 浙江三联环保科技股份有限公司 | A kind of sludge cleaning method for pyrolysis |
| CN111747630A (en) * | 2019-03-28 | 2020-10-09 | 佛山高明曦旺环保材料有限公司 | Excess sludge conditioning composition and application thereof |
| NL2023138B1 (en) * | 2019-05-15 | 2020-12-02 | Claris Case B V | METHOD AND SYSTEM FOR PROCESSING MERCURY SLUDGE |
| CN114349295A (en) * | 2021-12-29 | 2022-04-15 | 北京美斯顿科技开发有限公司 | Energy-saving and emission-reducing oil-containing slurry treatment system and method |
| CN114315062A (en) * | 2021-12-30 | 2022-04-12 | 上海大学无锡产业研究院 | Waste sludge dewatering method for water-based material |
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